Dyestuffs of the anthraquinone series



Patented Jan. 14, 1936 UNITED STATES PATENT OFFICE DYESTUFFS OF THE ANTHRAQUINONE SERIES Klaus Weinand and Ernst Kalckbrenner, Leverkusen I. G.-Werk, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application October 12, 1933, Serial No. 693,393. In Germany October 21, 1932 Claims. (01. 260-60) The present invention relates to new dyestuffs hearing at least one substituent which can be of the anthraquinone series, more particularly it replaced by a radical of an amine, the said subrelates to dyestufis of the probable general forstituent or substituents by the group A(NI-IRSO-a1k)n and then introducing into the molecule the sul- 5 wherein A stands for a radical of the anthrafoni acid group or groups; in case f the ulfid quinoneseries, R stands for a radical of the benthe oxidation to the lf id is performed zene Senes' alk Stands for an alkyl group and multaneously with the sulfonation process or. stands for one of the numbers one and two, and afterwards in a separate Step 1O t at least one sulfomc acld group 15 pres The introduction of the sulfonic acid group can em m the molecule be performed with the aid of one of the usual Our new dyestufis are obtainable according to sulfonafing agents, Such as oleum, or by substi g g a methods ai exampleifthflre m tuting halogen present in the molecule by the sule 1 prepared an raqulnone P acids ionic acid group by the action of neutral alkali contammg one 9 two subslltuents Whlch can be metal sulfite. The latter process is especially valreplaced by radicals of amines, such as halogen uable for the manufacture of compounds of the atoms or hydroxy groups. These substituted general formula. anthraquinone sulfonic acids are then caused to react with an amine of the general formula:

0 NHz--R-SO-alkyl,'wherein R means a radical of the benzene series, according to methods known per se, or the said substituted anthraquin- 8 lie one sulfonic acids are condensed with an amine radical of the 0f the general formula: NH2-RSalky1,' R benzene series 5 meaning a radical of the benzene series, in which case an oxidation of the sulfide to the sulfoxide must be carried out; this oxidation can be pera1ky1 =o formed either simultaneously with the condensation process or afterwards in a separate step. it being immaterial whether the sulfoxide group Another method of preparing our new dyeis formed prior to the introduction of the sulfonic 30 stuffs resides in first replacing in anthraquinone acid group or afterwards. Thus, for example, compounds free from a sulfonic acid group, but the following reactions may be performed:

('3' NH: 0 NH: C /([/L 35 v Br alkali metal S o v (1) sulfite 9'30 %0 alkyl alkyl 3 NH, (I? NH: 45

. Br gg? son; (2)

oxidizing agent g 50 IILIH 3 EH alkyl sum o The oxidation of the sulfide group; to the sulfoxide group in the compounds free from sulfonic acid groups can be performed, for example, with hydrogen peroxide or lead tetracetate in the presence of an organic solvent, such as glacial acetic acid, while in the case of compounds containing sulfonic acid groups there is favorably used water as solvent or diluent and hydrogen peroxide as oxidizing agent.

The new compounds are in form of their alkali metal salts generally crystalline, dark metallic lustrous powders, easily soluble in water. They are generally valuable dyestuffs for W001, dyeing wool from an acid bath generally bluish to green shades. Compared with analogously constituted anthraquinone amino condensation products they are distinquished by an improved solubility in water and capability of egalizing.

The invention is illustrated by the following examples, without being limited thereto:

Example 1 Parts by weight 1 -amino- 4 --bromoanthraquinone-2-sulfonic acid 10 4-aminophenyl-methylsulfoxide 10 Sodium bicarbonate 12 Cuprous chloride 0.5

are introduced into 150 parts by weight of water and heated at a temperature of about 70 to about 100 C. until a clear blue solution has formed. The dyestufi formed having in its free state the following formula:

USOIH to OH;

is separated as potassium salt in a crystalline form by the addition of potassium chloride. It dyes wool from an acid bath even blue shades.

By substituting the l-aminophenylmethylsulfoxide by 4-methyl-3-aminophenylmethylsulfoxide or by l-aminodiphenylsulfoxide or by 4-aminophenylethylsulfoxide there are obtained dyestuifs exerting similar properties.

Example 2.20 parts by weight of l-amino-Z, l-dibromoanthraquinone are heated in 200 parts by weight of 4-aminophenylmethylsulfide for about 8 to hours at about 170-190 C. with the addition of 10 parts by weight of sodium acetate, whereby the brown coloration of the solution turns to greenish-blue. By the addition of alcohol the 1-amino-2-bromo-4-(4-methylmercapto anilidoanthraquinone separates in a crystalline form.

10 parts by weight of the condensation product thus obtained are heated with 10 parts by weight of sodium sulfite in 100 parts by weight of water and with the addition of parts by weight of phenol/pyridine or -50 parts by weight of alcohol at 130-140 C. until the condensation product has entered into solution. The greenish-blue solution formed is treated at 60-'70 C. with about 5-10 parts by weight of an aqueous hydrogen-peroxide solution of 30% strength, whereby the coloration of the greenish-blue solution is turned to red. The dyestufi formed is identical with that described in Example 1.

The condensation product obtained from 1- amino-2,4-dibromoanthraquinone and it-aminophenylmethylsulfideobtained in accordance with paragraph 1 can be oxidized in glacial acetic acid or pyridine with hydrogenperoxide or lead tetracetate prior to the exchange of the 2-bromo-atom with'sulfite to a compound of the following constitution:

O NH:

ko (I? O and then treated with sulfite in the manner described.

SO-OH:

Example 3.10 parts by weight of leuco-quinacid. After cooling, the melt is stirred into about 200 parts by weight of an aqueous caustic soda lye of 30% strength, whereby the dyestuff formed separates in green crystals. The same are filtered and purified by recrystallizing from Water. The dyestuff having in the free state the following formula:

SOCHI o NH CH:

HOIS- c) IkH- on.

OOHl

is soluble in water with a green coloration and dyes wool from an acid bath green even shades.

Example 4.-20 parts by weight of quinizarin- 6-sulf0nic acid are introduced into 100 parts by weight of 4-aminophenylmethylsulfide, and at 60-70 C. 10 parts by weight of an aqueous hydrochloric acid of strength are added. At

this temperature part of the quimZarin-G-sulfonic acid is reduced by slowly adding 2 parts by weight of zinc dust. After this 5 parts by weight of boric acid are added, the temperature is raised to C. and kept at this temperature until a test portion is soluble in pyridine-water with a.yellowish green coloration.

To the melt alcohol is added and the condensation product formed having the following constitution:

H O 18-- \C/ is sucked off.

10 parts by weight of this product are treated in water with 5-10 parts by weight of hydrogenperoxide with the addition of sodium acetate at elevated temperature, until the product completely has entered into solution. By the addition of common salt the dyestuif of the following formula:

SOCH3 l mO-soom .The melt is diluted with 60 parts by weight of alcohol, and the green crystals separate dare filtered with suction. By treating the same with an oleum of 20% strength the 1.4-di-(4 methylmercapto)anilidoanthraquinone is transformed into a sulfonic acid which is diflicultly soluble in water and which dyes wool from an acid bath green shades.

In this sulfonic acid the mercapto group can be transformed into the sulfoxide group by oxidation with hydrogenperoxide in pyridine-water, whereby the dyestuff becomes more readily soluble in water and yields more even shades. In its free state the oxidized dyestuff corresponds probably to the following formula:

We claim:

1. Anthraquinone compounds of the general formula:

wherein A stands for a radical of the anthraquinone series, B stands for a radical of the benzene series, alk stands for an alkyl group and it stands for one of the numbers one and two, and wherein at least one sulfonic acid group is present in the molecule, being in form of their alkali metal salts generally crystalline dark metallic lustrous powders, easily soluble in water and dyeing wool from an acid bath generally bluish to greenish shades.

2. Anthraquinone compounds of the general formula:

wherein A stands for a radical of the anthraquinone series, R stands for a radical of the benzene series, alk stands for methyl or ethyl and n stands for one of the numbers one and two, and

wherein at least one sulfonic acid group is present in the molecule, being in form of their alkali metal salts generally crystalline dark metallic lustrous powders, easily soluble in water and'dyeing wool from an acid bath generally bluish to greenish shades.

3. The anthraquinone compound of the following formula:

% NHa C ll 1 O NH dyeing wool from an acid bath even blue shades.

4. The anthraquinone compound of the following formula:

NH- CH:

5. The anthraquinone compound 0'! the following formula:

y) l ra-040cm 10 dyeing wool from an acid bath even green shades.

KLAUS WEINAND. ERNST KALCKBRENNER. 

